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Patented A ug Z9, I933 j UNITED STATES i HALOGEN ANTHRAQUINONE i BENZACRIDONE' Mair" Albert Klinz, Mannheim, and-Karl: Koeberle and Erich Berthold, Ludwigshafen on'-the- 'Rhine, Germany, assignors to General Aniline Works, 'Inc., New York, N. Y.,,a corporation of, V

' Delaware j,

-No Drawing. Application October-23, 1930, 'Serial No. 490,810, and in Germany October 28, 1929 The present invention relates to newchloroanthraquinone-2.l (N) benzacridones and process of producingand halogenating the same.

, We have found that anthraquinone-ZltN-X- 5 benzacridones (a naphthoquinoneacridones) cor responding to the formula:

.0 a v a H in which the positionsmarked 'X and Y may-be substituted by chlorine, areparticularly valuable vat' dyestuffs dyeing from orange to blue red shades of remarkably good fastness against light 1 ,-i and atmospheric influences. The said dyestuffs are obtained by condensing a -l-hailogenanthraquinone-2carboxylic acid or' an' ester or'ar'nide' thereof with 2-chloroani1ine or such derivatives thereofas are substituted in the 3- orin" the 3A M; and ii-positions bychlorinegor by condensing '1- halogenanthraquinone with anthranil-ic acids substituted. by chlorine in correspondence-With the aforesaid chloroanilines; the resulting chlorophenyl-l-iminoanthraquinones having a carb ox ylic acid group in ortho position to the iminogroup being then converted into acridone derivatives I The condensation may be carried out injth'e presence or absence of dissolving or diluting media and/orof'acid-binding agents and prefer ably in the presence or condensing catalysts, as T halogenatin'g the said chloroanthraquinone-2,1

first. enters*the l position of the anthraquinever alsobe isolated and converted into the corresponding acridone derivatives in any k'no'wn and suitable n'ianner, asfo'r example by warming'with phosphorus halides orthion-yl chloride preferablyin an organic solvent or by treatment withacid 1 condensing agents, 'asuior eigample oleum, sulphuric acid or chlorosulphonic acid.

The B25-chlqroanthraquinone-zd (N -benzacridone is particularlyfsuitable for printing, w'her'eas; the-B225 theB245 dichloroanthraquinohe f 2'.1(N) v-benz acridones and the Bz2-L4.5-trichl oroanthraquinone-zl (N) benzacridone suitable for'dyeingpurposesJ 1 As already mentioned the saidchloroanthrae quinon'e-l l (N-) :-benzacridones dye orange to blue "are more red. shades of" excellent fastness. The shades obtained with thesaid dyestufis may be'varied without impairing their good f astness properties by (NX-benz acridone s" organic solvents whereby" wnmhnpg auhg1n "the absence; of halogenation' catalysts the halogen enters the benzene nu-' cIeus and-products are bbtainedidyeing fromor' angel to red 'shadesQwhen halogenating;however, in' the presenceof the said catalysts the halogen 55 one nucleus wherebythe shadesobtainedwith 7 these latter, dyestuffs-"are, generally speaking,"

more bluislyviz; from pink to"-blue red." Organic solvents whiehjmay be used in the halogenation' process comprise in particular aromatic solvents 1 of high boiling; point, such as for example nitrobenzene, chlorobenzfen'es; homologues of the said ivatives f: ben en naph hale e, niderivativeS. the on; ze ghalo nation, catalysts those usu ly e p oye may be usedior examp metals andmetal compounds, such asiron, mercury, anti-, mony andztheinehalides, or non -,metals ,"su ch a sulphurrs l niumand pa ti ular iodine.

The halogenanthraquinoneaz,Lbenzacridones are'usu'ally obtainedin very good. yields. and: in a. pure state. They may, howevienbepurified and separated from isomers by known methods if necessary, .as vfor example by crystallizationiromorganic solvents, by sublimation, by treatment with oxidizing agents, for example by i'treating their aqueous pastes with alkali metal hypo-l chlorites, or by way of their oxoniun salts. I

' The iolloyving examples will further fllustrate how this invention may be carried out in ac-1 tice, but the invention is not restricted to these examples. The parts are by weight.-

Example 1 57.2 parts of 1-chloroanthraquinone 2-carbox ylicacid are heated to boiling while stirring in 500 parts of trichlorcbenzene with 60 parts of 2.5 dichloroaniline and 25 parts of anhydrous oxalic acid until unchanged carboxylic, acid can no longerbe detected. The reaction mixture is then I allowed to cool and the reaction product which "to cool and worked up as; usual.

' trichloroanthraquinone -2.l-benzacridone mainly consists of 2.5'-dichlorophenyll-an-' out inthraquinone-2-carboxylic acid, separated crystalline form is filtered off.

parts of the reaction product are heated while stirring at between 160 and l'70 C. in 250. parts of nitrobenzene' with so parts of phosphorus pentachloride until a sample no. longer dissolves in alkalies. The reaction mixture is then allowed The B zzt-dichlor'oenthraquinone-Z.l-benzacridone separated in the form of yellow red uniform'ineedles dissolves in concentrated sulphuric acid to give an orange solution'and dyes-cotton clear yellow red shadesof very good fastness from a violetvat. 1

' "Ring-closure tolforrn the acridone derivative may also be effected by means of chlorosulphonic 36 H d s U Example 2 38 parts of the oenzyl ester of l-chloroanthra quinone-Q-carboxylic acid. are heated at between 18 0? and 200 C. whilestirring with 21 parts of 2.3.53-trichloroaniline, 1'3 parts of sodium acetate and 1 part of copper oxidein lO O partsof nitrobenzene until unchanged benzylester can no longerbe; detected. After cooling,the reaction product is filtered off and dissolved in the ten fold amount of concentrated sulphuric. acid.

After warming at 30 C. for one hour the reaction,

mixture is poured onto ice and tiled-(223L5- trichlorophenylamino) -anthraquinone -2 carboxylic acid thus produced. filtered offQl flThe ring closure to the acridone may be effected by known. methods, forexampleby means of chloros ulphonaic acid, phosphorus oxychloride or phosphorus pentachloride. The B22.45 trichloroanthraquie none2.l-benzacridone thus. obtained dissolves in concentrated sulphuric'acid to give a yellow red solution and dyes cotton from a violet vat clear red orange shades of excellent fastness against light and atmospheric influences. It crystallize's from solvents of high boiling point, such as nitrobenzene or trichlorobenzene, in yellow red nee-- dles. r

I Efra mp led I s 40 parts 7 of 3245-.dichldroanthraquinone-2.l-

benzacridone (obtainable f:acc,ording ;to Example 5) are heated to boiling while-stirring in, 400

. the vegetable fibre yellow red shades of verygood fastness against boiling with an alkaline solution- Example 4 from a .violet vat.

A' suspension of 572 parts of 1-chloroanthra quin'one-Z-carboxylic acid, 25 parts of anhydrous solves in alkalies. The reaction mixture isthen chloride in nitrobenaene.

usual manner.

, to about 180 CJafter the addition of 5 0 parts of. a phosphorus penta'chloride- The Bz l-fiedichloroi boric acid and 32partsof ortho-chloroaniline is heated to boiling, while stirring, in 500 parts of trichlorobenzene until a sample no longer dis allowed to cool and the B25chloroanthraquinone: 2.1-benzacridone filtered 01f. It crystallizes in felt-like red needles, which dissolve in concentrated sulphuric acidto give an orange solution andcwhich dye cotton from aviolet vat very fast red-shades. 1 I I The condensation may also be interrupted when the 1-ch1orophenylaminoanthraquinone-2- icarboxylic acid is formed, the acridone derivative being obtained therefrom in the usual manner, for instance by treatment with phosphorus penta- V Y Eztample 5 s 286 partsof l-chloroanthraquinone2-carboxy lic acid are. heated tobojiling' for 7 hours, while stirring, in 2900 parts of trichlorobenzene with 180 parts of 2.3- dich1oro-aniline and 125 parts of anhydrous oxalic acid. After cooling, the reaction product is filtered off and worked up in the parts of the l-,(2"-3'-dichlorophenyl)-1 aininoanthraquinone-2 carboxylic acid are Sus v pended-in200 parts of'nitrobenzene and heated anthraquihone-Z.l-benzacridone thus obtained is a red crystalline powder, dissolves in concentrated sulphuric acid to give a yellow red solution, dyes cotton from a violet vat fast bluish red shades and furnisheson the vegetable fibre excellently 10 fast red printings. I

Printing may be effected bymeans of a paste comprising an aqueous paste of the dyestuff, a thickening agentcontaining for example starch, n tragacanth and British gum, sodium forinaldehyde sulphoxylate, potash and glyc'eroLthe printingsbeing, steamed at about 100 C. with wet steam. a Example 6 39 parts of the B22,5-dichloroanthraquinoner: 2.1 benzacridone', obtainable according to Example 1 are slowlyheated, whilestirring, to between 90jand 1OOP C. in 300 parts of nitrobenzenieafter the addition ofl part of phosphorus, while passing chlorine into the reaction mixture which is :kept at thesaid temperature for several hours and then heated for a short. time to between and C. After cooling, the reactionproduct which separates -in, a crystalline form is filtered off. It is a; tetra-chloroderivative according to analysis, dissolves in concentrated sulphuric acid to give an orange solution'and dyes cotton very fast bluishred shades from a blue violet vat. u'Examplc 7 :36 parts, of B25-chloroanthraquinone- 2.1(N) benzacridone are heated at between and C. for several hours in 3 60 parts ofnitrobenzene after the additioriofAO parts of bromine and part of iodine. The reaction mixture is'allowed I to cool and'the l-1bromo-Bz3-bromo1-Bz5-chloro: anthraquinone-2.l (N) benz acridone separated in the form of blue red needles filtered oif. It dis: solves in concentratedsulphuric.acid to give an orange-solution and furnishes on cotton, when dyed at between 20,? and 30 C., red-violetshades from a violetvatr U r By chlorination by means of V chlorine. or

Bz3.5 trichloroanthraquinone z.1 (N) benzacriv done is obtained. i 7

What weclaim is:-

1 Chloroanthraquinone-2.I(N) henzacridones corresponding to the formula in which the positions marked and Y maybe substituted by chlorine, dyeingfrom orange to blue-red shades from violet vats and dissolving in concentrated sulphuric acid to give orange solu-v tions/ concentrated solution.

' shades and dissolving in rconcentrated 2. Bz5-chloroanthraquinone-2.1 (N) 'beniacridone crystallizing in -red needles, dyeing. cotton from a violet vat red shades; and dissolving in sulphuric acid to give an orange zacridone crystallizing in yellow red needles, dye

ing' cotton from a violet-vat clear yellow red H shades and V dissolving in concentrated sulphuric V 1 acidto give an orange solution, I v j 5. Bz2.4.5 trichloroanthraquinoned.1(N) '-ben-" zacridone crystallizing in yellow red needles, dissolving in concentrated sulphuricjacid to give a; yellow red solu'tion 'and dyeing cotton from a violet vat clear red orangeshades. n

- r 4 1 Y'YMAX ALBERT KUNZ. v

KQEBERLE.

BERTHOLD. 

